A carbonyl cobalt organic ionic liquid, its preparation method and application

Abstract

This invention discloses a cobalt carbonyl organic ionic liquid, its preparation method, and its applications. It uses a pyrazole cobalt carbonyl metal organic ionic liquid as the main catalyst to carry out a hydrogen esterification reaction in an organic alcohol solution of an epoxide compound under a carbon monoxide atmosphere to obtain β-hydroxypropionate. The pyrazole cobalt carbonyl metal organic ionic liquid of this invention has the advantages of high stability, high catalytic activity, and reusable catalyst. Using it as a catalyst, the hydrogen esterification reaction of ethylene oxide can be achieved under mild conditions, with a maximum ethylene oxide conversion rate of up to 95% and a maximum β-hydroxypropionate yield of up to 92%.

Description

Technical Field

[0001] This invention belongs to the field of fine chemicals, specifically relating to a cobalt carbonyl metal organic ionic liquid, its preparation method, and its application in the synthesis of β-hydroxypropionate. Background Technology

[0002] 1,3-Propanediol (1,3-PDO) is an important fine chemical used as a raw material in the production of antifreeze, plasticizers, preservatives, and emulsifiers. It is also widely used in the food, coatings, cosmetics, and pharmaceutical industries, and has a large market demand. 1,3-PDO is an important monomer for the synthesis of polyurethane. It can undergo a polyesterification reaction with terephthalic acid to obtain a novel polyester fiber material, polypropylene terephthalate (PTT). This type of polyester material has advantages such as light resistance, low water absorption, good stability, good resilience, easy biodegradability, and low environmental pollution, and has broad application prospects.

[0003] β-hydroxypropionate is a key intermediate in the synthesis of 1,3-PDO, and is currently mainly prepared via the hydrogen esterification reaction of ethylene oxide. The synthetic reaction is shown below: The development of novel catalysts is a key research focus in the hydrogen esterification reaction of epoxides. Shell used Co₂(CO)₈ / 1,10-phenanthroline as a catalyst and methyl tert-butyl ether as a solvent, achieving an ethylene oxide conversion of only 11% and a methyl 3-hydroxypropionate selectivity of 74%. Samsung later used Co as the main catalyst and nitrogen-containing heterocyclic compounds as ligands, increasing the ethylene oxide conversion to 94% and the methyl 3-hydroxypropionate selectivity to 78%. Many domestic research institutions have also studied catalysts for the hydrogen esterification reaction of epoxides. For example, Chen Jing et al. from the Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, achieved an ethylene oxide hydrogen esterification conversion of 87% and a methyl 3-hydroxypropionate yield of 87% using cobalt carbonyl as a catalyst; Zhang Ye et al. from Guangdong University of Petrochemical Technology, using cobalt carbonyl as a catalyst and adding imidazole as an auxiliary agent, increased the ethylene oxide hydrogen esterification conversion to 92% and the methyl 3-hydroxypropionate yield to 84%. Subsequently, research institutions such as Qingdao University of Science and Technology, Shanghai Research Institute of China Petroleum & Chemical Corporation, and Taiyuan University of Technology also conducted research on the catalyst system for the hydrogen esterification reaction of ethylene oxide.

[0004] However, existing cobalt carbonyl catalysts suffer from drawbacks such as air sensitivity, difficulty in storage, and challenges in recycling and reuse. Functionalized ionic liquids, as catalysts, possess both high catalytic activity and good stability. Cobalt carbonyl organometallic ionic liquids, as catalysts for the hydrogen esterification reaction of epoxides, offer a promising approach to addressing these issues and have attracted attention from researchers both domestically and internationally.

[0005] Patent CN 106995391 A discloses a method for preparing a 1,1,3,3-tetraalkylguanidine carbonyl cobalt metal organic ionic liquid catalyst, which maintains high catalytic activity and selectivity in the hydrogen esterification reaction of epoxides after six cycles.

[0006] Patent CN 107459451 A discloses the preparation of an ionic liquid catalyst containing the transition metal cobalt. Under the conditions of carbon monoxide pressure of 6.0 MPa and 75 °C, the conversion rate of ethylene oxide is 71% and the selectivity of methyl β-hydroxypropionate is 86%.

[0007] Patent CN 101973881B discloses the preparation of 1-R-3-methylimidazolium tetracarbonyl cobalt ionic liquid catalyst and its application in the synthesis of 1,3-PDO. The hydrogen esterification and hydrogenation reactions of epoxides can be completed in the same catalytic system, and the catalyst can be recycled.

[0008] This invention provides a pyrazole carbonyl cobalt metal organic ionic liquid, its preparation method, and its application in the synthesis of β-hydroxypropionate esters via the hydrogen esterification reaction of epoxides. Summary of the Invention

[0009] This invention develops a stable, non-toxic, highly catalytically active, and recyclable pyrazole carbonyl cobalt functionalized ionic liquid catalyst. The nitrogen-hydrogen bond in the pyrazole ionic liquid can stabilize the tetracarbonyl cobalt anion and can also act as a Brønsted acid to activate epoxides. Using it as a catalyst, the hydrogen esterification reaction of ethylene oxide can be achieved under mild conditions. It can be used for the preparation of various β-hydroxypropionates, especially methyl 3-hydroxypropionate.

[0010] To achieve the above objectives, the present invention adopts the following technical solution: The primary objective of this invention is to provide a pyrazole carbonyl cobalt functionalized ionic liquid catalyst.

[0011] The general structural formula of the pyrazole carbonyl cobalt metal organic ionic liquid is as follows: R is selected from alkyl, alkenyl, and aryl groups.

[0012] A second objective of this invention is to provide a method for preparing the pyrazole carbonyl cobalt functionalized ionic liquid catalyst.

[0013] The pyrazole carbonyl cobalt metal-organic ionic liquid is prepared by premixing a high-valence cobalt salt and a reducing agent in an organic alcohol, then placing the mixture in a sealed reactor and reacting it under a carbon monoxide atmosphere. After the reaction, the remaining powder in the system is removed by filtration. The filtrate is then reacted with the pyrazole ionic liquid under an inert gas atmosphere by stirring, the precipitate is removed by filtration, and the solvent is removed under vacuum to obtain the pyrazole carbonyl cobalt organic ionic liquid.

[0014] Furthermore, the high-valent cobalt salt is selected from one of CoCl2, CoBr2, Co(acac)2, Co3(PO4)2, Co(OAC)2, and CoCO3.

[0015] Furthermore, the organic alcohol is selected from one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol, and phenol.

[0016] Furthermore, X is selected from chlorine, bromine, or iodine.

[0017] Furthermore, the pyrazole ionic liquid is one of pyrazole hydrochloride, pyrazole bromate, and pyrazole iodide.

[0018] Further, the reducing agent is one or more of Fe, Co, Ni, Zn, Mn, LiAlH4, NaBH4, KBH4, and Na2S2O3, and its particle size is 300~1600 mesh.

[0019] Furthermore, the reaction temperature in the carbon monoxide atmosphere is 0~100 ℃, the pressure is 1~6 MPa, and the time is 1~24 h.

[0020] A third objective of this invention is to provide a method for synthesizing β-hydroxypropionate using the pyrazole carbonyl cobalt metal organic ionic liquid.

[0021] The method uses the pyrazole carbonyl cobalt metal organic ionic liquid as the main catalyst, an organic alcohol as the solvent and substrate, and an epoxide compound to carry out a hydrogen esterification reaction in a carbon monoxide atmosphere to prepare β-hydroxypropionate.

[0022] Furthermore, the organic alcohol is selected from one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol, and phenol.

[0023] Furthermore, in the reaction system, the concentration of the epoxide compound is 0.001 mol / L to 100 mol / L, and the concentration of the pyrazole carbonyl cobalt metal organic ionic liquid catalyst is 0.0001 mol / L to 100 mol / L. Furthermore, the hydrogen esterification reaction is carried out at a temperature of 40-80 °C, a pressure of 2-6 MPa, and a time of 1-24 h.

[0024] The beneficial effects of this invention are as follows: (1) The preparation method of pyrazole carbonyl cobalt metal organic ionic liquid is simple, it is stable to water and oxygen, has high catalytic efficiency, and the catalyst is easy to separate and recover after the reaction and can be recycled. (2) The product β-hydroxypropionate has extremely high application value, especially methyl 3-hydroxypropionate, which can be used in the large-scale production of 1,3-propanediol; (3) It eliminates the need to use low-cost cobalt precursors that are sensitive to air, have poor stability, are flammable, and are inconvenient to store and transport; (4) The reaction raw materials are bulk chemicals ethylene oxide and carbon monoxide, which are widely available and have mature preparation processes; (5) The conversion and selectivity of the ethylene oxide hydrogen esterification reaction can reach up to 95%, and the final yield of β-hydroxypropionate can reach up to 92%. Attached Figure Description

[0025] Figure 1 The infrared spectrum of [HMPz][Co(CO)4] in Example 2 is shown.

[0026] Figure 2 This is a gas chromatogram of the reaction stock solution in Example 18. Detailed Implementation

[0027] The pyrazole carbonyl cobalt metal-organic ionic liquid is prepared by premixing a high-valence cobalt salt and a reducing agent in an organic alcohol, then placing the mixture in a sealed reactor and reacting it under a carbon monoxide atmosphere. After the reaction, the remaining powder in the system is removed by filtration. The filtrate is then reacted with the pyrazole ionic liquid under an inert gas atmosphere by stirring, the precipitate is removed by filtration, and the solvent is removed under vacuum to obtain the pyrazole carbonyl cobalt organic ionic liquid.

[0028] Using the prepared pyrazole carbonyl cobalt metal organic ionic liquid as the main catalyst and an organic alcohol as the solvent and substrate, β-hydroxypropionate was prepared by hydrogen esterification reaction of epoxide in a carbon monoxide atmosphere.

[0029] The high-valent cobalt salt is selected from one of CoCl2, CoBr2, Co(acac)2, Co3(PO4)2, Co(OAC)2, and CoCO3.

[0030] The organic alcohol is selected from one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol, and phenol.

[0031] The pyrazole ionic liquid is one of pyrazole hydrochloride, pyrazole bromine, and pyrazole iodide.

[0032] The reducing agent is one or more of Fe, Co, Ni, Zn, Mn, LiAlH4, NaBH4, KBH4, and Na2S2O3, with a particle size of 300-1600 mesh.

[0033] The reaction, carried out in a carbon monoxide atmosphere, has a reaction temperature of 0–100 °C, a pressure of 0.1–6 MPa, and a reaction time of 1–24 h.

[0034] In the reaction system, the concentration of the epoxy compound is 0.001 mol / L to 100 mol / L, and the concentration of the pyrazole carbonyl cobalt organic ionic liquid catalyst is 0.0001 mol / L to 100 mol / L.

[0035] The hydrogen esterification reaction is carried out at a temperature of 40-80 °C, a pressure of 2-6 MPa, and a time of 1-24 h.

[0036] To make the content of this invention easier to understand, the technical solution of this invention will be further described below with reference to specific embodiments, but this invention is not limited thereto.

[0037] Example 1 A 100 mL high-pressure reactor was used. First, 1.0 mmol CoCl₂ and 6 mmol of reducing agent Mn powder (325 mesh) were mixed in 20 mL of methanol. The mixture was then placed into the reactor and sealed. The gas in the reactor was replaced three times with CO to fill the reactor with CO. The system pressure was then adjusted to 4.0 MPa, and the mixture was heated to 40 °C for 15 h. After the reaction, the remaining powder was removed by filtration. The filtrate was then mixed with 1-pentylpyrazole hydrochloride (HAPzCl) (HAPzCl was synthesized using the same method as above). ACSSustainableChem.Eng. 2018, 6 The reaction mixture (2574−2582) was stirred under a nitrogen atmosphere for 6 h. After the reaction, the precipitate was removed by filtration, and the solvent was removed under vacuum to obtain [HAPz][Co(CO)4]. In a 100 mL autoclave, pyrazole carbonyl cobalt organic ionic liquid [HAPz][Co(CO)4] (1.0 mmol), methanol (20 mL), and ethylene oxide (200 mmol) were added. The gas in the autoclave was replaced with CO three times to fill the autoclave with CO. Then the system pressure was adjusted to 5.0 MPa, heated to 40 °C, and reacted for 15 h. After the reaction, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0038] Example 2 A 100 mL high-pressure reactor was used. First, 1.0 mmol CoCl₂ was mixed with 6 mmol of reducing agent Mn powder (325 mesh) in 20 mL of methanol. This mixture was then placed into the reactor and sealed. The gas in the reactor was replaced three times with CO to fill the reactor completely. The system pressure was then adjusted to 4.0 MPa, and the mixture was heated to 40 °C for 15 h. After the reaction, the remaining powder was removed by filtration. The filtrate was then mixed with 1-methylpyrazole hydrochloride (HMPzCl) (HMPzCl was synthesized using the same method as above). ACSSustainableChem.Eng. 2018, 6 (Consistent with 2574−2582) The reaction was stirred under a nitrogen atmosphere for 6 h. After the reaction, the precipitate was removed by filtration, and the solvent was removed under vacuum to obtain [HMPz][Co(CO)4]. In a 100 mL autoclave, [HMPz][Co(CO)4] (1.0 mmol), methanol (20 mL), and ethylene oxide (200 mmol) were added. The gas in the autoclave was replaced with CO three times to fill the autoclave with CO. Then the system pressure was adjusted to 5.0 MPa, heated to 40 °C, and reacted for 15 h. After the reaction, the original reaction solution was analyzed by GC. The results are shown in Table 1.

[0039] Example 3 A 100 mL high-pressure reactor was used. First, 1.0 mmol of CoCl₂ was mixed with 6 mmol of reducing agent Mn powder (325 mesh) in 20 mL of methanol. This mixture was then placed into the reactor and sealed. The gas in the reactor was replaced three times with CO to fill the reactor with CO. The system pressure was then adjusted to 4.0 MPa, and the mixture was heated to 40 °C for 15 h. After the reaction, the remaining powder was removed by filtration. The filtrate was then mixed with 1-ethylpyrazole hydrochloride (HEPzCl) (HEPzCl was synthesized using the same method as above). ACSSustainableChem.Eng. 2018, 6 The reaction mixture (2574−2582) was stirred under a nitrogen atmosphere for 6 h. After the reaction, the precipitate was removed by filtration, and the solvent was removed under vacuum to obtain [HEPz][Co(CO)4]. In a 100 mL autoclave, [HEPz][Co(CO)4] (1.0 mmol), methanol (20 mL), and ethylene oxide (200 mmol) were added. The gas in the autoclave was replaced with CO three times to fill the autoclave with CO. Then, the system pressure was adjusted to 5.0 MPa, and the mixture was heated to 40 °C for 15 h. After the reaction, the original reaction solution was analyzed by GC. The results are shown in Table 1.

[0040] Example 4 A 100 mL high-pressure reactor was used. First, 1.0 mmol of CoCl₂ was mixed with 6 mmol of reducing agent Mn powder (325 mesh) in 20 mL of methanol. This mixture was then placed into the reactor and sealed. The gas in the reactor was replaced three times with CO to fill the reactor with CO. The system pressure was then adjusted to 4.0 MPa, and the mixture was heated to 40 °C for 15 h. After the reaction, the remaining powder was removed by filtration. The filtrate was then mixed with 1-propylpyrazole hydrochloride (HPPzCl) (HPPzCl was synthesized using the same method as above). ACSSustainableChem.Eng. 2018, 6 (Consistent with 2574−2582) The reaction was stirred under a nitrogen atmosphere for 6 h. After the reaction, the precipitate was removed by filtration, and the solvent was removed under vacuum to obtain [HPPz][Co(CO)4]. In a 100 mL autoclave, [HPPz][Co(CO)4] (1.0 mmol), methanol (20 mL), and ethylene oxide (200 mmol) were added. The gas in the autoclave was replaced with CO three times to fill the autoclave with CO. Then the system pressure was adjusted to 5.0 MPa, heated to 40 °C, and reacted for 15 h. After the reaction, the original reaction solution was analyzed by GC. The results are shown in Table 1.

[0041] Example 5 A 100 mL high-pressure reactor was used. First, 1.0 mmol of CoCl₂ was mixed with 6 mmol of reducing agent Mn powder (325 mesh) in 20 mL of methanol. This mixture was then placed into the reactor and sealed. The gas in the reactor was replaced three times with CO to fill the reactor completely. The system pressure was then adjusted to 4.0 MPa, and the mixture was heated to 40 °C for 15 h. After the reaction, the remaining powder was removed by filtration. The filtrate was then mixed with 1-butylpyrazole hydrochloride (HBPzCl) (HBPzCl synthesis method is referenced). ACSSustainableChem.Eng. 2018, 6 The reaction mixture (2574−2582) was stirred under a nitrogen atmosphere for 6 h. After the reaction, the precipitate was removed by filtration, and the solvent was removed under vacuum to obtain [HBPz][Co(CO)4]. In a 100 mL autoclave, [HBPz][Co(CO)4] (1.0 mmol), methanol (20 mL), and ethylene oxide (200 mmol) were added. The gas in the autoclave was replaced with CO three times to fill the autoclave with CO. Then, the system pressure was adjusted to 5.0 MPa, and the mixture was heated to 40 °C and reacted for 15 h. After the reaction, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0042] Example 6 A 100 mL high-pressure reactor was used. First, 1.0 mmol of CoCl₂ and 6 mmol of reducing agent Mn powder (325 mesh) were mixed in 20 mL of methanol. The mixture was then placed into the reactor and sealed. The gas in the reactor was replaced three times with CO to fill the reactor with CO. The system pressure was then adjusted to 4.0 MPa, and the mixture was heated to 40 °C for 15 h. After the reaction, the remaining powder in the system was removed by filtration. The filtrate was then mixed with 1-pentylpyrazole bromate (HAPzBr) (HAPzBr was synthesized using the same method as above). ACSSustainableChem.Eng. 2018, 6 The reaction mixture (2574−2582) was stirred under a nitrogen atmosphere for 6 h. After the reaction, the precipitate was removed by filtration, and the solvent was removed under vacuum to obtain [HAPz][Co(CO)4]. In a 100 mL autoclave, [HAPz][Co(CO)4] (1.0 mmol), methanol (20 mL), and ethylene oxide (200 mmol) were added. The gas in the autoclave was replaced with CO three times to fill the autoclave with CO. Then, the system pressure was adjusted to 5.0 MPa, and the mixture was heated to 40 °C and reacted for 15 h. After the reaction, the original reaction solution was analyzed by GC. The results are shown in Table 1.

[0043] Example 7 A 100 mL high-pressure reactor was used. First, 1.0 mmol of CoCl₂ and 6 mmol of reducing agent Mn powder (325 mesh) were mixed in 20 mL of methanol. The mixture was then placed into the reactor and sealed. The gas in the reactor was replaced three times with CO to fill the reactor with CO. The system pressure was then adjusted to 4.0 MPa, and the mixture was heated to 40 °C and reacted for 15 h. After the reaction was complete, the remaining powder in the system was removed by filtration. The filtrate was then mixed with 1-pentylpyrazole iodate (HAPzI) (HAPzI was synthesized using the same method as above). ACSSustainableChem.Eng. 2018, 6 The reaction mixture (2574−2582) was stirred under a nitrogen atmosphere for 6 h. After the reaction, the precipitate was removed by filtration, and the solvent was removed under vacuum to obtain [HAPz][Co(CO)4]. In a 100 mL autoclave, [HAPz][Co(CO)4] (1.0 mmol), methanol (20 mL), and ethylene oxide (200 mmol) were added. The gas in the autoclave was replaced with CO three times to fill the autoclave with CO. Then, the system pressure was adjusted to 5.0 MPa, and the mixture was heated to 40 °C and reacted for 15 h. After the reaction, the original reaction solution was analyzed by GC. The results are shown in Table 1.

[0044] Example 8 The Mn powder used in Example 1 was replaced with Fe powder, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0045] Example 9 The Mn powder used in Example 1 was replaced with Co powder, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0046] Example 10 The Mn powder used in Example 1 was replaced with Ni powder, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0047] Example 11 The Mn powder used in Example 1 was replaced with Zn powder, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0048] Example 12 The Mn powder used in Example 1 was replaced with LiAlH4, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0049] Example 13 The Mn powder used in Example 1 was replaced with NaBH4, the catalyst preparation temperature was 0-5℃, and other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0050] Example 14 The Mn powder used in Example 1 was replaced with KBH4, the catalyst preparation temperature was 0-5℃, and other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0051] Example 15 The CoCl2 used in Example 1 was replaced with CoBr2, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0052] Example 16 The CoCl2 used in Example 1 was replaced with Co(acac)2, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0053] Example 17 The CoCl2 used in Example 1 was replaced with Co3(PO4)2, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0054] Example 18 The CoCl2 used in Example 1 was replaced with Co(OAc)2, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0055] Example 19 The CoCl2 used in Example 1 was replaced with CoCO3, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0056] Example 20 The amount of CoCl2 used in Example 1 was changed from 1 mmol to 0.6 mmol, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0057] Example 21 The amount of CoCl2 used in Example 1 was changed from 1 mmol to 0.8 mmol, while other operating conditions remained unchanged. The original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0058] Example 22 The amount of CoCl2 used in Example 1 was changed from 1 mmol to 2 mmol, while other operating conditions remained unchanged. The original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0059] Example 23 The hydrogen esterification reaction temperature in Example 1 was changed from 40℃ to 50℃, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0060] Example 24 The hydrogen esterification reaction temperature in Example 1 was changed from 40℃ to 70℃, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0061] Example 25 The hydrogen esterification reaction temperature in Example 1 was changed from 40℃ to 80℃, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0062] Example 26 The hydrogen esterification reaction pressure in Example 1 was changed from 5.0 MPa to 2.0 MPa, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0063] Example 27 The hydrogen esterification reaction pressure in Example 1 was changed from 5.0 MPa to 3.0 MPa, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0064] Example 28 In Example 1, the amount of methanol used in the hydrogen esterification reaction was changed from 20 mL to 40 mL, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0065] Example 29 The hydrogen esterification reaction time in Example 1 was changed from 15 h to 4 h, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0066] Example 30 The hydrogen esterification reaction time in Example 1 was changed from 15 h to 8 h, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0067] Example 31 The hydrogen esterification reaction time in Example 1 was changed from 15 h to 12 h, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0068] Example 32 The hydrogen esterification reaction time in Example 1 was changed from 15 h to 16 h, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0069] Example 33 The hydrogen esterification reaction time in Example 1 was changed from 15 h to 24 h, while other operating conditions remained unchanged. After the reaction was completed, the original reaction solution was analyzed by GC, and the results are shown in Table 1.

[0070] Example 34 After the reaction in Example 1 was completed, the solvent and methyl β-hydroxypropionate were removed by vacuum distillation of the reaction solution. The remaining liquid was transferred back into a 100 mL high-pressure reactor. Methanol (20 mL) and ethylene oxide (200 mmol) were added. The gas in the reactor was replaced with CO three times to fill the reactor with CO. Then the system pressure was adjusted to 5.0 MPa, heated to 40 °C, and reacted for 15 h. After the reaction was completed, the original reaction solution was analyzed by GC. The results are shown in Table 1.

[0071] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

Claims

1. The application of a cobalt carbonyl organic ionic liquid in the synthesis of β-hydroxypropionate, characterized in that: The preparation method of the cobalt carbonyl organic ionic liquid includes: using a 100 mL high-pressure reactor, first mixing 1.0 mmol CoCl2 with 6 mmol reducing agent Mn powder in 20 mL methanol, then filling the reactor and sealing it, replacing the gas in the reactor with CO three times to fill the reactor with CO, then adjusting the system pressure to 4.0 MPa, heating to 40℃, and reacting for 15 h. After the reaction, filtering out the remaining powder in the system, stirring the filtrate and 1-pentylpyrazole hydrochloride HAPzCl under a nitrogen atmosphere for 6 h, filtering out the precipitate after the reaction, and removing the solvent under vacuum to obtain [HAPz][Co(CO)4]; The method for using the cobalt carbonyl organic ionic liquid in the synthesis of β-hydroxypropionate includes: adding 1.0 mmol of pyrazole cobalt carbonyl organic ionic liquid [HAPz][Co(CO)4], 20 mL of methanol, and 200 mmol of ethylene oxide to a 100 mL autoclave; replacing the gas in the autoclave with CO three times to fill the autoclave with CO; then adjusting the system pressure to 5.0 MPa; heating to 40 °C; and reacting for 15 h.

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